General Procedure and Instrument Data: Infrared and Raman Spectroscopy

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IMPORTANCE OF CATALYSIS

The global chemical industry of today is driven by catalysis to such an extent that one cannot underestimate the importance of catalytic processes to the wealth creation of any country. For example, it has been estimated that around 20% of the entire US Gross National Product is generated through the use of catalytic processes. These are instrumental in fields that include, but are not limited to, the production of fuels, petrochemicals, pharmaceuticals, polymers and agrichemicals, as well as environmentally favourable technologies such as catalytic converters.

HOMOGENEOUS AND HETEROGENEOUS CATALYSIS

Within catalytic research there are two main different types of catalytic processes that are utilised and investigated, namely homogeneous and heterogeneous catalysis. In homogeneous catalysis the reactions occur at metal centres and the metal complex catalysts, promoters, reagents and products are all soluble in the reaction medium. Conversely, heterogeneous catalytic reactions occur on a surface with many metal centres and the reagents (normally in the liquid or gas phase) are led over or through the catalyst, which in fact aids the separation of products from the reaction process ].

CATALYTIC STEPS

All catalytic processes proceed via a number of interlinked steps [1]:
1. activation of the metal centre or generation of the active catalyst
2. movement of the reactants to the active centre and their binding and activation
3. making and breaking of the reactant bonds to generate new intermediate species
4. liberation of these intermediate species as products, with the return of the catalyst to a state where it is ready to begin the cycle again.

OVERVIEW OF CATALYTIC DESIGN

Before detailing and discussing specific catalytic processes, it is important for one to appreciate that the study of any catalyst is driven by a number of key elements than can be traced back to a specific market need. This is illustrated in the Figure 1.1.

Abstract
Acknowledgements
CHAPTER 1 INTRODUCTION
1.1 IMPORTANCE OF CATALYSIS
1.2 HOMOGENEOUS AND HETEROGENEOUS CATALYSIS
1.3 CATALYSIS AND TRANSITION METALS
1.4 CATALYTIC STEPS
1.5 OVERVIEW OF CATALYTIC DESIGN
1.6 ETHYLENE OLIGOMERISATIONS
1.6.1 1-Hexene
1.6.2 1-Octene
1.7 PROJECT OUTLINE
1.7.1 Monomeric and Dimeric States
1.7.2 Ligands
1.7.3 Characterisation and Analysis
1.7.3.1 X-ray Crystallography
1.7.3.2 Infrared and Raman Spectroscopy
1.7.3.3 NMR Spectroscopy
1.7.3.4 Computational Studies
1.7.3.5 Mass Spectrometry
1.8 EXPERIMENTAL
1.8.1 Safety Remarks
1.8.2 General Remarks
1.8.3 Standard Colour Changes
1.8.4 Synthesis of the Starting Material [CrCl3(thf)3]
1.8.5 General Procedure and Instrument Data: Infrared and Raman Spectroscopy
1.8.6 General Procedure and Instrument Data: X-ray Crystallography
1.8.7 General Procedure and Instrument Data: 1 H NMR Scale Experiments
1.8.8 General Procedure and Instrument Data:Computational Studies
1.8.9 General Procedure and Instrument Data: Mass Spectrometry
CHAPTER 2 CHROMIUM(III) MONODENTATE NITROGEN LIGAND CHEMISTRY
2.1 INTRODUCTION
2.2 CATEGORY ONE: SEQUENTIAL ADDITION OF PYRIDI
2.2.1 Visual Analysis
2.2.2 Infrared and Raman Spectroscopy
2.2.3 Computational Study
2.2.4 NMR Spectroscopy
2.2.5 X-ray Crystallography
2.2.5.1 [CrCl3(py)3]
2.2.5.2 [Hpy][CrCl4(py)2]
2.2.6 Mass Spectrometry
2.3 CATEGORY TWO: BULKY SUBSTITUENTS
2.3.1 Infrared Spectroscopy
2.3.1.1 Region 3114–2804 cm-1
2.3.1.2 Region 1660–1247 cm-1
2.3.1.3 Region 1219–448 cm-1
2.3.1.4 Region 415–214 cm-1
2.3.2 X-ray Crystallography
2.4 CATEGORY THREE: PARA–SUBSTITUTED PYRIDINES
2.4.1 Infrared and Raman Spectroscopy
2.4.1.1 Region 3321–2869 cm-1
2.4.1.2 Region 1638–1045 cm-1
2.4.1.3 Region 1030–499 cm-1
2.4.1.4 Ligand substituents
2.4.1.5 Bond Strength
2.4.1.6 Region 488–213 cm-1
2.4.1.7 Concluding remarks
2.4.2 Computational Studies
2.4.3 NMR of [CrCl3(thf)3] and three equivalents of pyphenyl
2.4.4 Mass Spectrometry
2.4.5 X-ray Crystallography
2.4.5.1 [CrCl3(pytb)3]
2.5 EXPERIMENTAL
2.5.1 Synthesis of [CrCl3(py)(thf)2] (1) and [CrCl3(py)2(thf)] (2)
2.5.2 Synthesis of [CrCl3(py)3] (3)
2.5.3 Synthesis of [CrCl3(2,6-dibromopy)3] and [CrCl3(py)2(DMF)] (5).
2.5.4 Synthesis of [CrCl3(pyNH2)3] (6)
2.5.5 Synthesis of [CrCl3(pytb)3] (7)
2.5.6 Synthesis of [CrCl3(pyphenyl)3] (8)
2.5.7 Synthesis of [CrCl3(pyOH)3]
CHAPTER 3 CHROMIUM(III) BIDENTATE NITROGEN LIGAND CHEMISTRY
3.1 INTRODUCTION
3.2 SYNTHESIS
3.3 SYNTHETIC ROUTE TO PRODUCT FORMATION
3.4 INFRARED AND RAMAN SPECTROSCOPY
3.4.1 Region 3329–2291 cm-1
3.4.2 Region 1652–1104 cm-1
3.4.3 Region 1104–522 cm-1
3.4.3.1 Pyridine Specific
3.4.3.2 Bipyridine Specific
3.4.3.3 Thf Specific
3.4.3.4 Pyridinium Specific
3.4.4 Region 451–221 cm-1
3.5 COMPUTATIONAL STUDIES
3.5.1 [CrCl3(bipy)(thf)]
3.5.2 [CrCl3(bipy)(H2O)]
3.5.3 [CrCl3(bipy)(CH3CN)]
3.5.4 [CrCl3(bipy)(py)]
3.5.5 [CrCl3(bipy)(pyphenyl)]
3.5.6 [HpyNH2][CrCl4(bipy)]
3.5.7 HOMO and LUMO orbitals of the calculated complexes
3.6 NMR SPECTROSCOPY
3.7 MASS SPECTROMETRY
3.8 X-RAY CRYSTALLOGRAPHY
3.8.1 Solubility and Crystal Synthesis
3.8.2 [CrCl3(bipy)(H2O]
3.8.3 [HpyNH2][CrCl4(bipy)]
3.8.4 [CrCl2(bipy)2][Cl]·H2O
3.9 SYNTHETIC ROUTE CONCLUSIONS
3.10 EXPERIMENTAL
3.10.1 Synthesis of [CrCl3(bipy)(thf)] (9)
3.10.2 Synthesis of [CrCl3(bipy)(CH3CN)] (10)
3.10.3 Synthesis of [CrCl3(bipy)(py)] (11)
3.10.4 Synthesis of [CrCl3(bipy)(pyNH2)] (12)
3.10.5 Synthesis of [CrCl3(bipy)(pytb)] (13)
3.10.6 Synthesis of [CrCl3(bipy)(pyphenyl)] (14)
3.10.7 Synthesis of [CrCl3(bipy)(H2O)] (16)
3.10.8 Synthesis of [CrCl2(bipy)2][Cl]·H2O (17)
CHAPTER 4 CHROMIUM(III) BIDENTATE PHOSPHORUS CHEMISTRY
4.1 INTRODUCTION
4.2 SYNTHESIS
4.3 SYNTHETIC ROUTE TO PRODUCT FORMATION
4.4 INFRARED AND RAMAN SPECTROSCOPY
4.4.1 Region 3313–2863 cm-1
4.4.2 Region 1651–1045 cm-1
4.4.3 Region 1026–519 cm-1
4.4.4 Region 495–215 cm-1
4.5 COMPUTATIONAL STUDY
4.6 NMR SPECTROSCOPY
4.7 MASS SPECTROMETRY
4.8 X-RAY CRYSTALLOGRAPHY
4.8.1 [Hpyphenyl][CrCl4(dppe)]
4.9 EXPERIMENTAL
4.9.1 Synthesis of [CrCl3(dppe)(thf)] / [Cr(dppe)Cl2(µ-Cl)]2 (18)
4.9.2 Synthesis of [CrCl3(dppe)(py)] (19)
4.9.3 Synthesis of [CrCl3(dppe)(pyNH2)] (20)
4.9.4 Synthesis of [CrCl3(dppe)(pytb)] (21)
4.9.5 Synthesis of [CrCl3(dppe)(pyphenyl)] (22)
CHAPTER 5 CHROMIUM(III) BIDENTATE NITROGEN / PHOSPHORUS MIXED LIGAND CHEMISTRY
5.1 INTRODUCTION
5.2 2-PYRIDYLDIPHENYLPHOSPHINE AND [CrCl3(thf)3]
5.2.1 Synthesis
5.3 2-DIPHENYLPHOSPHINOETHYLAMINE AND [CrCl3(thf)3
5.3.1 Synthesis
5.3.2 Infrared and Raman Spectroscopy
5.3.2.1 Region 3380–2867 cm-1
5.3.2.2 Region 1652–1117 cm-1
5.3.2.3 Region 1117–500 cm-1
5.3.2.4 Region 500–200 cm-1
5.3.3 Computational Study
5.3.4 Mass Spectrometry
5.4 EXPERIMENTAL
5.4.1 Synthesis of [CrCl3(dppea)(thf)] / [Cr(dppea)Cl2(µ-Cl)]2 (24)
5.4.2 Synthesis of [CrCl3(dppea)(py)] (25)
5.4.3 Synthesis of [CrCl3(dppea)(pyNH2)] (26)
5.4.4 Synthesis of [CrCl3(dppea)(pytb)] (27)
5.4.5 Synthesis of [CrCl3(dppea)(pyhenyl)] (28)
CHAPTER 6 FUTURE WORK AND CONCLUSIONS
6.1 FUTURE WORK
6.2 CONCLUSION